US20250208467A1 - Wavelength conversion member and manufacturing method therefor - Google Patents

Wavelength conversion member and manufacturing method therefor Download PDF

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US20250208467A1
US20250208467A1 US18/847,677 US202318847677A US2025208467A1 US 20250208467 A1 US20250208467 A1 US 20250208467A1 US 202318847677 A US202318847677 A US 202318847677A US 2025208467 A1 US2025208467 A1 US 2025208467A1
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wavelength conversion
conversion member
quantum dots
modification part
member according
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Takuma Arikawa
Masafumi Kuramoto
Takayoshi Wakaki
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Nichia Corp
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Nichia Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials

Definitions

  • the present disclosure relates to a wavelength conversion member and a method of producing the same.
  • WO 2016/039079 proposes a functional laminated film that includes: a functional layer laminate having a functional layer containing quantum dots, and two gas barrier films; and an end surface protective layer covering the end surface of the functional layer.
  • An object of one aspect of the present disclosure is to provide: a wavelength conversion member in which discoloration from an end portion is inhibited; and a method of producing the same.
  • a first aspect is a wavelength conversion member including a laminate that includes: a wavelength conversion layer containing quantum dots; and two barrier layers each laminated on one of main surfaces of the wavelength conversion layer and on the other main surface.
  • the barrier layers each have a first modification part on at least a portion of their end surfaces, and the wavelength conversion layer has a second modification part on at least a portion of its end surface.
  • the second modification part is at least partially exposed on an end surface of the laminate.
  • a second aspect is a method of producing a wavelength conversion member, the method including: preparing a laminated sheet that includes a wavelength conversion layer containing quantum dots, and two barrier layers each laminated on one of main surfaces of the wavelength conversion layer and on the other main surface; and cutting the laminated sheet by irradiation with a laser beam intersecting the main surfaces of the laminated sheet to obtain a singulated laminate.
  • the irradiation with the laser beam is performed at a laser beam frequency that is 5 kHz to 30 kHz, a scanning speed that is 50 mm/s to 100 mm/s, and a laser beam output that is 3.4 W to 100 W.
  • a wavelength conversion member in which discoloration from an end portion is inhibited and a method of producing the same can be provided.
  • FIG. 1 is an example of an X-ray diffraction pattern of the nanoparticle precursor according to Reference Example 1.
  • FIG. 2 is an example of a transmission electron micrograph of the quantum dots according to Reference Example 1.
  • FIG. 3 is a schematic cross-sectional view illustrating an aspect of an end portion of a laminate.
  • FIG. 4 is an example of a reflected electron image of a cut surface of the wavelength conversion member according to Comparative Example 1, in which the cut surface was made using a cutting machine.
  • FIG. 5 is an example of a reflected electron image of a cut surface of the wavelength conversion member according to Example 3, in which the cut surface was made using a laser beam.
  • FIG. 6 is an example of a fluorescence micrograph of a cross-section of an end portion of the wavelength conversion member according to Comparative Example 1, in which the cross-section was made using a cutting machine.
  • FIG. 7 is an example of a fluorescence micrograph of a cross-section of an end portion of the wavelength conversion member according to Example 3, in which the cross-section was made using a laser beam.
  • FIG. 8 is a schematic cross-sectional view illustrating an aspect of a wavelength conversion member.
  • step used herein encompasses not only a discrete step but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.
  • an indicated amount of the component contained in the composition means, unless otherwise specified, a total amount of the plural substances existing in the composition.
  • values exemplified for the numerical range can be arbitrarily selected and combined.
  • the relationships between color names and chromaticity coordinates, the relationships between wavelength ranges of light and color names of monochromatic light, and the like conform to JIS Z8110.
  • a “half-value width” of a phosphor means, in an emission spectrum of a light emitting material, a wavelength width at which the emission intensity is 50% relative to the maximum emission intensity (full-width at half maximum; FWHM).
  • FWHM full-width at half maximum
  • layer used herein encompasses, when a region having the layer is observed, not only a case where the layer is formed on the entirety of the region but also a case where the layer is formed on only a part of the region.
  • laminate used herein refers to stacking of layers, where two or more of the layers may be bonded with each other, or may be detachable from each other.
  • wavelength conversion layer for “wavelength conversion layer”, “barrier layer”, and the like, the same term may be used before and after cutting. It is noted here that the dimensions, the positional relations, and the like of members illustrated in the drawings may be exaggerated for clarity of description.
  • the same names and symbols denote the same members or members of the same quality, and a detailed description thereof is omitted as appropriate.
  • the elements constituting the present invention may take a mode where plural elements are constituted by the same member so that a single member doubles as the plural elements or, conversely, a function of a single member may be shared and realized by plural members.
  • a description of a layer, a film, or the like to be “on” or “above” other component encompasses not only a case where the layer, the film, or the like is “directly on” the other component, but also a case where another component is provided therebetween.
  • a component arranged “on” another component encompasses not only a case where the component is arranged on the upper side of another component, but also a case where the component is arranged on the lower side of another component.
  • Embodiments of the present invention will now be described in detail. It is noted here, however, that the below-described embodiments are merely examples of a wavelength conversion member and a method of producing the same that embody the technical ideas of the present invention, and the present invention is not limited to the below-described wavelength conversion member and method of producing the same.
  • a wavelength conversion member includes a laminate that includes: a wavelength conversion layer containing quantum dots; and two barrier layers each laminated on one of main surfaces of the wavelength conversion layer and on the other main surface.
  • the barrier layers each have a first modification part on at least a portion of their end surfaces, and the wavelength conversion layer has a second modification part on at least a portion of its end surface.
  • the second modification part is at least partially exposed on an end surface of the laminate.
  • the wavelength conversion member may include the laminate, and an end surface covering layer that is arranged to cover the end surface of the laminate.
  • the first modification part and the second modification part are each formed by, for example, irradiation with a laser beam, whereby discoloration from an end portion of the wavelength conversion member with time is inhibited.
  • the first modification part and the second modification part that are capable of sufficiently inhibiting the intrusion of moisture and the like are formed by irradiating the laser beam under such conditions that, for example, the second modification part is at least partially exposed on the end surface of the laminate.
  • the first modification part covers boundaries between the respective barrier layers and the wavelength conversion layer, and this inhibits the effects of the external environment through the boundaries.
  • the laminate has two opposing main surfaces and an end surface that surrounds the periphery of the main surfaces in the lamination direction.
  • the opposing main surfaces each correspond to a main surface of the respective barrier layers.
  • the end surface of the laminate is arranged along the periphery of the main surfaces and composed of a surface intersecting the main surfaces.
  • the end surface of the laminate may be substantially perpendicular to, for example, the main surfaces of the laminate.
  • the periphery of the main surfaces of the laminate may be surrounded by four flat end surfaces, or by end surfaces including at least one curved end surface.
  • the wavelength conversion layer contains quantum dots.
  • quantum dots used herein refers to semiconductor crystal particles having a particle size of several nanometers to several tens of nanometers. When the size of a substance is reduced to the order of nanometers, electrons in the substance can exist only in a limited state. This makes the state of the electrons discrete, and the band-gap varies depending on the particle size.
  • the quantum dots absorb light and emit a light having a wavelength corresponding to their band-gap energy. Therefore, the emission wavelength of the quantum dots can be controlled by controlling the particle size, the crystal composition, and the like, and the quantum dots are allowed to function as a wavelength conversion substance.
  • the quantum dots contained in the wavelength conversion layer may have a particle size of, for example, 50 nm or less.
  • the particle size of the quantum dots may be preferably 1 nm to 20 nm, 1.6 nm to 8 nm, or 2 nm to 7.5 nm.
  • each semiconductor nanoparticle constituting the quantum dots refers to the length of the longest line segment among those line segments that connect any two points on the circumference of the particle observed in a transmission electron microscope (TEM) image and pass through the center of the particle.
  • An average particle size of semiconductor nanoparticles means a value obtained by measuring the particle size of each measurable semiconductor nanoparticle observed in a TEM image and calculating the arithmetic mean of the thus measured values.
  • the length of the short axis is regarded as the particle size of each particle.
  • the term “rod-shaped particle” used herein refers to a particle that is observed to have, for example, a quadrangular shape such as a rectangular shape elongated in one direction (a cross-section has a circular, elliptical, or polygonal shape), an elliptical shape, or a polygonal shape (e.g., a pencil-like shape) when the surface including the long axis is observed, and in which a ratio of the length of the long axis with respect to the length of the short axis is higher than 1.2.
  • the length of the long axis means the length of the longest line segment among those line segments connecting any two points on the circumference of the particle and, for a rod-shaped particle having a rectangular or polygonal shape, the length of the long axis means the length of the longest line segment among those line segments that are parallel to the longest side among all sides defining the circumference of the particle and connect any two points on the circumference of the particle.
  • the length of the short axis means the length of the longest line segment that is perpendicular to the line segment defining the length of the long axis, among those line segments connecting any two points on the circumference of the particle.
  • the average particle size of the semiconductor nanoparticles is determined by measuring the particle size for all measurable semiconductor nanoparticles observed in a TEM image captured at a magnification of ⁇ 50,000 to ⁇ 150,000, and calculating the arithmetic mean of the thus measured values.
  • the “measurable” particles are those particles whose outlines are entirely observable in a TEM image. Accordingly, in a TEM image, a particle that is partially not included in the captured area and thus appears to be “cut” is not a measurable particle.
  • the average particle size is determined using the single TEM image.
  • the number of nanoparticles contained in the single TEM image is small, another TEM image is further captured at a different position, and the particle size is measured for 100 or more particles contained in two or more TEM images to determine the average particle size.
  • the quantum dots include perovskite quantum dots, chalcopyrite quantum dots, and indium phosphide (InP) quantum dots.
  • the perovskite quantum dots may contain, for example, a compound represented by the following Formula (1):
  • M 1 represents a first element including at least one selected from the group consisting of Cs, Rb, K, Na, and Li;
  • a 1 represents a non-metal cation including at least one selected from the group consisting of an ammonium ion, a formamidinium ion, a guanidinium ion, an imidazolium ion, a pyridinium ion, a pyrrolidinium ion, and a protonated thiourea ion;
  • M 2 represents a second element including at least one selected from the group consisting of Ge, Sn, Pb, Sb, and Bi;
  • X represents an anion or a ligand, which includes at least one selected from the group consisting of a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a thiocyanate, an isothiocyanate, and a sulfide
  • the ammonium ion may be represented by, for example, the following Formula (A-1).
  • the formamidinium ion may be represented by, for example, the following Formula (A-2).
  • the guanidinium ion may be represented by, for example, the following Formula (A-3).
  • the protonated thiourea ion may be represented by, for example, the following Formula (A-4).
  • the imidazolium ion may be represented by, for example, the following Formula (A-5).
  • the pyridinium ion may be represented by, for example, the following Formula (A-6).
  • the pyrrolidinium ion may be represented by, for example, the following Formula (A-7).
  • Rs each independently represent at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a halogen atom, and a pseudo-halogen.
  • any two Rs may be linked with each other to form a nitrogen-containing aliphatic ring having 3 to 6 carbon atoms.
  • the perovskite quantum dots that contain a compound having a composition represented by the above-described Formula (1) emit a green light or a red light when irradiated with a light emitted from a light source.
  • the perovskite quantum dots may emit a light having a peak emission wavelength in a range of 475 nm to 560 nm when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm, preferably a light source having a peak emission wavelength in a range of, for example, 380 nm to 500 nm.
  • the peak emission wavelength of the perovskite quantum dots emitting the green light may be in a range of preferably 510 nm to 560 nm, 520 nm to 560 nm, or 525 nm to 535 nm.
  • the perovskite quantum dots may emit a light having a peak emission wavelength in a range of 600 nm to 680 nm when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 320 nm to 545 nm, preferably a light source having a peak emission wavelength in a range of, for example, 320 nm to 450 nm.
  • the peak emission wavelength of the perovskite quantum dots emitting the red light may be in a range of preferably 610 nm to 670 nm, 620 nm to 660 nm, or 625 nm to 635 nm.
  • the half-value width may be, for example, 35 nm or less, preferably 30 nm or less, or 25 nm or less.
  • the perovskite quantum dots may exhibit band-edge emission in the emission spectrum.
  • the chalcopyrite quantum dots may contain a first semiconductor containing silver (Ag), indium (In), gallium (Ga), and sulfur (S), and may be configured such that a second semiconductor containing Ga and S is arranged on the surfaces of the chalcopyrite quantum dots.
  • the second semiconductor may further contain Ag.
  • the first semiconductor may be a semiconductor that has a chalcopyrite-type structure containing Ag, In, Ga, and S.
  • a deposit containing the second semiconductor may be arranged on the surfaces of particles containing the first semiconductor, and the particles containing the first semiconductor may be covered with the deposit containing the second semiconductor.
  • the chalcopyrite quantum dots may have a core-shell structure in which, for example, a particle containing the first semiconductor constitutes a core and a deposit containing the second semiconductor is arranged as a shell on the surface of the core.
  • a particle containing the first semiconductor constitutes a core
  • a deposit containing the second semiconductor is arranged as a shell on the surface of the core.
  • the first semiconductor contains at least Ag that may be partially substituted such that the first semiconductor further contains at least one of copper (Cu), gold (Au), or an alkali metal (hereinafter, may be denoted as M a ), or the first semiconductor may be composed of substantially Ag.
  • substantially used herein indicates that a ratio of the number of atoms of Ag-substituting elements other than Ag is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower, with respect to a total number of atoms of Ag and the Ag-substituting elements other than Ag.
  • the first semiconductor may contain substantially Ag and an alkali metal as constituent elements.
  • substantially indicates that a ratio of the number of atoms of the Ag-substituting elements other than Ag and the alkali metal is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower, with respect to a total number of atoms of Ag, the alkali metal, and the Ag-substituting elements other than Ag and the alkali metal.
  • the alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
  • the first semiconductor may have a composition represented by, for example, the following Formula (2a):
  • the second semiconductor may be arranged on the surfaces of the chalcopyrite quantum dots.
  • the second semiconductor may contain a semiconductor having a larger band-gap energy than that of the first semiconductor.
  • the second semiconductor may be a semiconductor composed of substantially Ga and S.
  • the second semiconductor may be a semiconductor composed of substantially Ag, Ga, and S.
  • substantially indicates that, when a total number of atoms of all elements contained in a semiconductor containing Ga and S or a semiconductor containing Ag, Ga, and S is taken as 100%, a ratio of the number of atoms of elements other than Ga and S or elements other than Ag, Ga, and S is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower.
  • the chalcopyrite quantum dots of the first aspect may exhibit band-edge emission having a peak emission wavelength in a wavelength range of 475 nm to 560 nm (e.g., green color) when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm, and the peak emission wavelength may be in a range of preferably 510 nm to 550 nm, 515 nm to 545 nm, or 525 nm to 535 nm.
  • the half-value width may be, for example, 45 nm or less, preferably 40 nm or less, 35 nm or less, or 30 nm or less.
  • the half-value width may be, for example, 15 nm or more.
  • the chalcopyrite quantum dots may contain a third semiconductor containing copper (Cu), silver (Ag), indium (In), gallium (Ga), and sulfur (S), and may be configured such that a fourth semiconductor containing Ga and S is arranged on the surfaces of the chalcopyrite quantum dots.
  • the fourth semiconductor may further contain Ag.
  • the third semiconductor may be a semiconductor that has a chalcopyrite-type structure containing Cu, Ag, In, Ga, and S.
  • a deposit containing the fourth semiconductor may be arranged on the surfaces of particles containing the third semiconductor, and the particles containing the third semiconductor may be covered with the deposit containing the fourth semiconductor.
  • the chalcopyrite quantum dots may have a core-shell structure in which, for example, a particle containing the third semiconductor constitutes a core and a deposit containing the fourth semiconductor is arranged as a shell on the surface of the core.
  • a particle containing the third semiconductor constitutes a core
  • a deposit containing the fourth semiconductor is arranged as a shell on the surface of the core.
  • the third semiconductor contains at least Ag and Cu that may be partially substituted such that the third semiconductor also contains gold (Au) and an alkali metal (M a ), or the first semiconductor may be composed of substantially Ag.
  • the third semiconductor may contain substantially Ag, Cu, and an alkali metal as constituent elements.
  • the term “substantially” used herein indicates that a ratio of the number of atoms of elements other than Ag, Cu, and the alkali metal is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower, with respect to a total number of atoms of Ag, Cu, the alkali metal, and the elements other than Ag, Cu, and the alkali metal.
  • the third semiconductor may have a composition represented by, for example, the following Formula (2b):
  • substantially indicates that, when a total number of atoms of all elements contained in a semiconductor containing Ga and S or a semiconductor containing Ag, Ga, and S is taken as 100%, a ratio of the number of atoms of elements other than Ga and S or elements other than Ag, Ga, and S is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower.
  • the chalcopyrite quantum dots of the second aspect may exhibit band-edge emission having a peak emission wavelength in a wavelength range of 600 nm to 680 nm (e.g., red color) when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm, and the peak emission wavelength may be in a range of preferably 610 nm to 670 nm, 620 nm to 660 nm, or 625 nm to 635 nm.
  • a peak emission wavelength in a wavelength range of 600 nm to 680 nm (e.g., red color) when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm
  • the peak emission wavelength may be in a range of preferably 610 nm to 670 nm, 620 nm to
  • the half-value width may be, for example, 70 nm or less, preferably 65 nm or less, 60 nm or less, or 30 nm or less.
  • the half-value width may be, for example, 15 nm or more.
  • the chalcopyrite quantum dots may contain a fifth semiconductor containing silver (Ag), gallium (Ga), and selenium (Se), and may be configured such that a sixth semiconductor containing zinc (Zn) and S (sulfur) is arranged on the surfaces of the chalcopyrite quantum dots.
  • the fifth semiconductor contains at least Ag, Ga, and Se that may be partially substituted such that the fifth semiconductor also contains indium (In) and sulfur (S).
  • the sixth semiconductor may further contain at least one of Ga or Se.
  • the fifth semiconductor may be a semiconductor that has a chalcopyrite-type structure containing Ag, Ga, and Se.
  • a deposit containing the sixth semiconductor may be arranged on the surfaces of particles containing the fifth semiconductor, and the particles containing the fifth semiconductor may be covered with the deposit containing the sixth semiconductor.
  • the chalcopyrite quantum dots may have a core-shell structure in which, for example, a particle containing the fifth semiconductor constitutes a core and a deposit containing the sixth semiconductor is arranged as a shell on the surface of the core.
  • the fifth semiconductor contains at least Ag, Ga, and Se that may be partially substituted such that the fifth semiconductor also contains indium (In) and sulfur (S).
  • the sixth semiconductor may be arranged on the surfaces of the chalcopyrite quantum dots.
  • the sixth semiconductor may contain a semiconductor having a larger band-gap energy than that of the fifth semiconductor.
  • the sixth semiconductor may be a semiconductor composed of substantially Zn and S.
  • substantially used herein indicates that, when a total number of atoms of all elements contained in a semiconductor containing Zn and S is taken as 100%, a ratio of the number of atoms of elements other than Zn and S is, for example, 10% or lower, preferably 5% or lower, more preferably 1% or lower.
  • the indium phosphide (InP) quantum dots are one form of semiconductor nanoparticles containing a Group III-V semiconductor.
  • Examples of the Group III-V semiconductor include AlN, AlP, AlAs, AlSb, GaAs, GaP, GaN, GaSb, InN, InAs, InP, InSb, TiN, TiP, TiAs, and TiSb.
  • Group III-V quantum dots on the surfaces of semiconductor nanoparticles containing a Group III-V semiconductor, a deposit containing a seventh semiconductor different from the Group III-V semiconductor constituting the semiconductor nanoparticles may be arranged, and the particles containing the Group III-V semiconductor may be covered with the deposit containing the seventh semiconductor.
  • the Group III-V quantum dots may have a core-shell structure in which, for example, a particle containing the Group III-V semiconductor constitutes a core and a deposit containing the seventh semiconductor is arranged as a shell on the surface of the core.
  • the seventh semiconductor may be a semiconductor having a larger band-gap energy than that of the Group III-V semiconductor.
  • Examples of a combination of the Group III-V semiconductor and the seventh semiconductor include InP/ZnS, GaP/ZnS, InN/GaN, InP/CdSSe, InP/ZnSeTe, InGaP/ZnSe, InGaP/ZnS, InP/ZnSTe, InGaP/ZnSTe, and InGaP/ZnSSe.
  • the Group III-V semiconductor (e.g., indium phosphide) quantum dots may emit a green light or a red light when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 500 nm.
  • the Group III-V semiconductor quantum dots emitting a green light may exhibit band-edge emission having a peak emission wavelength in a range of 475 nm to 580 nm when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm, preferably a light source having a peak emission wavelength in a range of, for example, 380 nm to 500 nm.
  • the peak emission wavelength may be in a range of preferably 510 nm to 570 nm, 520 nm to 560 nm, or 525 nm to 535 nm.
  • the Group III-V semiconductor quantum dots emitting a red light may exhibit band-edge emission having a peak emission wavelength in a range of 600 nm to 680 nm when irradiated with a light emitted from a light source having a peak emission wavelength in a range of, for example, 380 nm to 545 nm.
  • the peak emission wavelength may be in a range of preferably 610 nm to 670 nm, 620 nm to 660 nm, or 625 nm to 635 nm.
  • the half-value width may be, for example, 70 nm or less, preferably 65 nm or less, 60 nm or less, or 30 nm or less.
  • the half-value width may be, for example, 15 nm or more.
  • the quantum dots may also contain other quantum dots in addition to the perovskite quantum dots, the chalcopyrite quantum dots, and the indium phosphide quantum dots.
  • the other quantum dots include particles containing at least one selected from the group consisting of Group II-VI semiconductors, Group IV-VI semiconductors, and Group IV semiconductors.
  • Group II-VI semiconductors include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe.
  • Group IV-VI semiconductors include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe.
  • Specific examples of the Group IV semiconductors include Si, Ge, SiC, and SiGe.
  • a surface modifier may be arranged on the surfaces of the quantum dots.
  • Specific examples of the surface modifier include: an amino alcohol having 2 to 20 carbon atoms; an ionic surface modifier; a nonionic surface modifier; a nitrogen-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms; a sulfur-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms; an oxygen-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms; a phosphorus-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms; and a halide containing at least one selected from the group consisting of Group 2 elements, Group 12 elements, and Group 13 elements.
  • These surface modifiers may be used singly, or in combination of two or more different kinds thereof.
  • the amino alcohol used as the surface modifier may be any compound as long as it has an amino group and an alcoholic hydroxy group and contains a hydrocarbon group having 2 to 20 carbon atoms.
  • the number of carbon atoms in the amino alcohol is preferably 10 or less, more preferably 6 or less.
  • the hydrocarbon group constituting the amino alcohol may be derived from a hydrocarbon such as a linear, branched, or cyclic alkane, alkene, or alkyne.
  • the expression “derived from a hydrocarbon” used herein means that the hydrocarbon group is formed by removing at least two hydrogen atoms from the hydrocarbon.
  • amino alcohol examples include amino ethanol, amino propanol, amino butanol, amino pentanol, amino hexanol, and amino octanol.
  • amino group of the amino alcohol binds to the surface of the respective semiconductor nanoparticles and the hydroxy group is exposed on the particle outermost surface on the opposite side, as a result of which the polarity of the semiconductor nanoparticles is changed, and the dispersibility in alcohol-based solvents (e.g., methanol, ethanol, propanol, and butanol) is improved.
  • alcohol-based solvents e.g., methanol, ethanol, propanol, and butanol
  • the ionic functional group may be either cationic or anionic, and the ionic surface modifier preferably contains at least a cationic group.
  • specific examples of the surface modifier and a surface modification method reference can be made to, for example, Chemistry Letters, Vol. 45, pp 898-900, 2016.
  • the ionic surface modifier may be, for example, a sulfur-containing compound containing a tertiary or quaternary alkylamino group.
  • the number of carbon atoms of the alkyl group in the alkylamino group may be, for example, 1 to 4.
  • the sulfur-containing compound may also be an alkyl or alkenylthiol having 2 to 20 carbon atoms.
  • Specific examples of the ionic surface modifier include hydrogen halides of dimethylaminoethanethiol, halogen salts of trimethylammonium ethanethiol, hydrogen halides of dimethylaminobutanethiol, and halogen salts of trimethylammonium butanethiol.
  • nonionic surface modifier used as the surface modifier examples include nitrogen-containing compounds, sulfur-containing compounds, and oxygen-containing compounds, which have a nonionic functional group containing an alkylene glycol unit, an alkylene glycol monoalkyl ether unit, or the like.
  • the number of carbon atoms of the alkylene group in the alkylene glycol unit may be, for example, 2 to 8, and it is preferably 2 to 4. Further, the number of repeating alkylene glycol units may be, for example, 1 to 20, and it is preferably 2 to 10.
  • the nitrogen-containing compounds, the sulfur-containing compounds, and the oxygen-containing compounds, which constitute the nonionic surface modifier may contain an amino group, a thiol group, and a hydroxy group, respectively.
  • Specific examples of the nonionic surface modifier include methoxytriethyleneoxy ethanethiol and methoxyhexaethyleneoxy ethanethiol.
  • Examples of the nitrogen-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms include amines and amides.
  • Examples of the sulfur-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms include thiols.
  • Examples of the oxygen-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms include carboxylic acids, alcohols, ethers, aldehydes, and ketones.
  • Examples of the phosphorus-containing compound containing a hydrocarbon group having 4 to 20 carbon atoms include trialkyl phosphines, triaryl phosphines, trialkyl phosphine oxides, and triaryl phosphine oxides.
  • Examples of the halide containing at least one selected from the group consisting of Group 2 elements, Group 12 elements, and Group 13 elements include magnesium chloride, calcium chloride, zinc chloride, cadmium chloride, aluminum chloride, and gallium chloride.
  • the quantum dots contained in the wavelength conversion layer may contain at least one selected from the group consisting of first quantum dots having a peak emission wavelength in a wavelength range of 475 nm to 560 nm and second quantum dots having a peak emission wavelength in a wavelength range of 600 nm to 680 nm.
  • the quantum dots may contain at least one kind of the first quantum dots and at least one kind of the second quantum dots.
  • the first quantum dots may contain at least one selected from the group consisting of, for example, perovskite quantum dots, indium phosphide quantum dots, and the chalcopyrite quantum dots of the first aspect.
  • the first quantum dots may contain at least one selected from the group consisting of perovskite quantum dots and the chalcopyrite quantum dots of the first aspect.
  • the second quantum dots may contain at least one selected from the group consisting of, for example, perovskite quantum dots, the chalcopyrite quantum dots of the second aspect, and indium phosphide quantum dots.
  • the second quantum dots may contain at least one selected from the group consisting of the chalcopyrite quantum dots of the second aspect and indium phosphide quantum dots.
  • the wavelength conversion layer constituting the laminate may be provided in a single layer, or two or more layers.
  • one of the wavelength conversion layers may contain the first quantum dots, while the other wavelength conversion layer may contain the second quantum dots.
  • the wavelength conversion layer may contain, for example, chalcopyrite quantum dots emitting a green light and chalcopyrite quantum dots emitting a red light.
  • the wavelength conversion layer may contain chalcopyrite quantum dots emitting a green light and indium phosphide quantum dots emitting a red light.
  • the wavelength conversion layer may contain perovskite quantum dots emitting a green light and indium phosphide quantum dots emitting a red light.
  • the wavelength conversion layer may contain perovskite quantum dots emitting a green light and chalcopyrite quantum dots emitting a red light.
  • the wavelength conversion layer may include, for example, a layer that contains chalcopyrite quantum dots emitting a green light, and a layer that contains chalcopyrite quantum dots emitting a red light.
  • the wavelength conversion layer may include a layer that contains chalcopyrite quantum dots emitting a green light, and a layer that contains indium phosphide quantum dots emitting a red light.
  • the wavelength conversion layer may include a layer that contains perovskite quantum dots emitting a green light, and a layer that contains indium phosphide quantum dots emitting a red light.
  • the wavelength conversion layer may include a layer that contains perovskite quantum dots emitting a green light, and a layer that contains chalcopyrite quantum dots emitting a red light.
  • the wavelength conversion layer may contain at least one phosphor as a light emitting material other than the quantum dots.
  • a garnet-based phosphor such as an aluminum-garnet phosphor can be used.
  • the garnet-based phosphor include cerium-activated yttrium-aluminum-garnet phosphors, and cerium-activated lutetium-aluminum-garnet phosphors.
  • garnet-based phosphor for example, a nitrogen-containing calcium aluminosilicate-based phosphor activated by europium and/or chromium, a silicate-based phosphor activated by europium, a ⁇ -SiAlON-based phosphor, a nitride-based phosphor such as a CASN-based or SCASN-based phosphor, a rare earth nitride-based phosphor such as a LnSi 3 Ni-based or LnSiAlON-based phosphor, an oxynitride-based phosphor such as a BaSi 2 O 2 N 2 :Eu-based or Ba 3 Si 6 O 12 N 2 :Eu-based phosphor, a sulfide-based phosphor such as a CaS-based, SrGa 2 S 4 -based, or ZnS-based phosphor, a chlorosilicate-based phosphor, a
  • plural elements listed separately with commas (,) in a formula representing the composition of a phosphor mean that at least one of the plural elements is contained in the composition. Further, in a formula representing the composition of a phosphor, the part preceding a colon (:) represents a host crystal, and the part following the colon (:) represents an activation element.
  • the wavelength conversion layer may contain, for example, chalcopyrite quantum dots emitting a green light and a manganese-activated fluoride complex phosphor emitting a red light, or a perovskite quantum dots emitting a green light and a manganese-activated fluoride complex phosphor emitting a red light.
  • the wavelength conversion layer may include a layer that contains chalcopyrite quantum dots emitting a green light, and a layer that contains a manganese-activated fluoride complex phosphor emitting a red light.
  • the wavelength conversion layer may include a layer that contains perovskite quantum dots emitting a green light, and a layer that contains a manganese-activated fluoride complex phosphor emitting a red light.
  • the wavelength conversion layer may also contain a cured resin in addition to the quantum dots.
  • the cured resin may be a cured product of the below-described photocurable composition.
  • the content ratio of the quantum dots in the wavelength conversion layer may be, for example, 0.01% by mass to 1.0% by mass, preferably 0.05% by mass to 0.5% by mass, or 0.1% by mass to 0.5% by mass, with respect to a total amount of the cured resin.
  • the content ratio of the quantum dots is 0.01% by mass or more, a sufficient emission intensity tends to be obtained at the time of irradiating the wavelength conversion layer with light, whereas when the content ratio of the quantum dots is 1.0% by mass or less, aggregation of the quantum dots is inhibited, so that color unevenness tends to be reduced.
  • the photocurable composition forming the cured resin may contain, for example, a (meth)acrylic compound.
  • This (meth)acrylic compound may be a monofunctional (meth)acrylic compound having a single (meth)acryloyl group in one molecule, or a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule.
  • the (meth)acrylic compound may be used singly, or in combination of two or more kinds thereof, and a monofunctional (meth)acrylic compound and a polyfunctional (meth)acrylic compound may be used in combination.
  • the term “(meth)acrylic compound” used herein encompasses an acrylic compound, a methacrylic compound, and a mixture thereof, and the same applies to similar notations.
  • the monofunctional (meth)acrylic compound include: (meth)acrylic acid; alkyl (meth)acrylates whose alkyl group has 1 to 18 carbon atoms, such as methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylate compounds having an aromatic ring, such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; aminoalkyl (meth)acrylates, such as N,N-dimethylaminoethyl (meth)acrylate; (meth)acrylate compounds having an alicyclic group, such as cyclohexyl (meth)acrylate, dicyclopentanyl (
  • polyfunctional (meth)acrylic compound examples include: alkylene glycol di(meth)acrylates, such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; tri(meth)acrylate compounds, such as trimethylolpropane tri(meth)acrylate and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and tetra(meth)acrylate compounds, such as trimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.
  • alkylene glycol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(me
  • the photocurable composition may contain, for example, a (meth)allyl compound.
  • the (meth)allyl compound may be a monofunctional (meth)allyl compound having a single (meth)allyl group in one molecule, or a polyfunctional (meth)allyl compound having two or more (meth)allyl groups in one molecule.
  • the (meth)allyl compound may be used singly, or in combination of two or more kinds thereof, and a monofunctional (meth)allyl compound and a polyfunctional (meth)allyl compound may be used in combination.
  • the (meth)allyl compound preferably contains a polyfunctional (meth)allyl compound.
  • a ratio of the polyfunctional (meth)allyl compound with respect to a total amount of the (meth)allyl compound may be, for example, 80% by mass or more, preferably 90% by mass or more, or 100% by mass.
  • polyfunctional (meth)allyl compound examples include di(meth)allyl cyclohexanedicarboxylate, di(meth)allyl maleate, di(meth)allyl adipate, di(meth)allyl phthalate, di(meth)allyl isophthalate, di(meth)allyl terephthalate, glycerin di(meth)allyl ether, trimethylolpropane di(meth)allyl ether, pentaerythritol di(meth)allyl ether, 1,3-di(meth)allyl-5-glycidyl isocyanurate, tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl trimellitate, tetra(meth)allyl pyromellitate, 1,3,4,6-tetra (meth)allyl glycoluril, 1,3,4,6-tetra(meth)allyl-3a-
  • the polyfunctional (meth)allyl compound preferably contains at least one selected from the group consisting of tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, di(meth)allyl phthalate, di(meth)allyl isophthalate, di(meth)allyl terephthalate, and di(meth)allyl cyclohexanedicarboxylate, more preferably is tri(meth)allyl isocyanurate.
  • the content ratio of the (meth)allyl compound may be, for example, 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass, or 10% by mass to 15% by mass, with respect to a total amount of the curable composition.
  • the content ratio of the (meth)allyl compound is 1% by mass or more, the heat resistance and the moist heat resistance of the cured product tend to be further improved, whereas when the content ratio of the (meth)allyl compound is 30% by mass or less, the adhesion of the cured product tend to be further improved.
  • the photocurable composition preferably contains an alkyleneoxy group-containing compound having an alkyleneoxy group and a polymerizable reactive group. This tends to make the preparation of a high-viscosity curable composition easier and, at the time of preparing the curable composition that is an emulsion of a resin component and a dispersoid by stirring a mixture of these components, unification of the dispersoid caused by aggregation tends to be inhibited. As a result, a high dispersibility of the dispersoid is maintained, so that the wavelength conversion member tends to have excellent emission intensity.
  • the alkyleneoxy group-containing compound preferably has an ester group.
  • the alkyleneoxy group-containing compound may have one or more ester groups, and preferably has two or more ester groups.
  • the alkyleneoxy group-containing compound preferably has two or more polymerizable reactive groups, and more preferably has two polymerizable reactive groups.
  • the adhesion, the heat resistance, and the moist heat resistance of the cured product tend to be further improved.
  • the polymerizable reactive groups include functional groups having an ethylenic double bond, more specifically a (meth)acryloyl group.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 or more carbon atoms, more preferably an alkyleneoxy group having 2 or 3 carbon atoms, still more preferably an alkyleneoxy group having 2 carbon atoms.
  • the alkyleneoxy group-containing compound may have a single kind of alkyleneoxy group, or two or more kinds of alkyleneoxy groups.
  • the alkyleneoxy group-containing compound may be a polyalkyleneoxy group-containing compound that has a polyalkyleneoxy group containing plural alkyleneoxy groups.
  • the alkyleneoxy group-containing compound may have 2 to 30 alkyleneoxy groups, preferably 2 to 20, 3 to 10, or 3 to 5 alkyleneoxy groups.
  • the alkyleneoxy group-containing compound preferably has a bisphenol structure.
  • a bisphenol structure By this, excellent moist heat resistance tends to be obtained.
  • the bisphenol structure include a bisphenol A structure and a bisphenol F structure, between which a bisphenol A structure is preferred.
  • alkyleneoxy group-containing compound examples include: alkoxyalkyl (meth)acrylates, such as butoxyethyl (meth)acrylate; polyalkylene glycol monoalkyl ether (meth)acrylates, such as diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monobutyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, heptapropylene glycol monomethyl ether (meth)acrylate, and tetraethylene glycol monoethyl ether (meth)acrylate; polyalkylene glycol monoaryl ether (meth)acrylates, such as hexaethylene glycol
  • alkyleneoxy group-containing compound ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and propoxylated ethoxylated bisphenol A di(meth)acrylate are preferred, and ethoxylated bisphenol A di(meth)acrylate is more preferred.
  • alkyleneoxy group-containing compounds may be used singly, or in combination of two or more kinds thereof.
  • the content ratio of the alkyleneoxy group-containing compound in the photocurable composition may be, for example, 0.5% by mass to 10% by mass, preferably 1% by mass to 8% by mass, or 1.5% by mass to 5% by mass, with respect to a total amount of the photocurable composition.
  • the content ratio of the alkyleneoxy group-containing compound is 0.5% by mass or more, the viscosity of the photocurable composition tends to be increased, whereas when the content ratio of the alkyleneoxy group-containing compound is 10% by mass or less, the viscosity of the photocurable composition is not excessively increased, so that excellent production efficiency of the wavelength conversion member tends to be obtained.
  • the photopolymerization initiator include: aromatic ketone compounds, such as benzophenone, N,N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4,4′-bis(dimethylamino)benzophenone (also referred to as “Michler's ketone”), 4,4′-bis(diethylamino)benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy
  • the content ratio of the photopolymerization initiator may be, for example, 0.1% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, or 0.5% by mass to 1.5% by mass, with respect to a total amount of the photocurable composition.
  • the content ratio of the photopolymerization initiator is 0.1% by mass or more, the photocurable composition tends to have sufficient sensitivity, whereas when the content ratio of the photopolymerization initiator is 5% by mass or less, effects on the hue of the photocurable composition and deterioration in the storage stability of the photocurable composition tend to be inhibited.
  • the curable composition may also contain a liquid medium.
  • This liquid medium refers to a medium that is in a liquid state at room temperature (25° C.).
  • the liquid medium include ketone solvents, ether solvents, carbonate solvents, ester solvents, aprotic polar solvents, alcohol solvents, glycol monoether solvents, aromatic hydrocarbon solvents, terpene solvents, saturated aliphatic monocarboxylic acids, and unsaturated aliphatic monocarboxylic acids.
  • the curable composition may contain any of these liquid media singly, or two or more kinds of these liquid media in combination.
  • the content ratio of the liquid medium in the photocurable composition may be, for example, 1% by mass to 10% by mass, preferably 4% by mass to 10% by mass, or 4% by mass to 7% by mass, with respect to a total amount of the photocurable composition.
  • the photocurable composition may contain other components, such as a polymerization inhibitor, a silane coupling agent, a surfactant, and adhesion promoter, and an antioxidant.
  • the photocurable composition may contain each of these other components singly, or two or more kinds of each of these other components in combination.
  • the photocurable composition may further contain quantum dots.
  • the photocurable composition containing quantum dots can be prepared by, for example, mixing the quantum dots, a (meth)acrylic compound, an alkyleneoxy group-containing compound, a photopolymerization initiator and, if necessary, the above-described components by a conventional method.
  • the quantum dots are preferably mixed in a state of, for example, a quantum dot dispersion in which the quantum dots are dispersed in a monofunctional (meth)acrylate compound having an alicyclic group and a liquid medium.
  • the wavelength conversion layer can be formed by curing the photocurable composition containing quantum dots.
  • the wavelength conversion layer containing quantum dots and a cured resin can be formed by, for example, applying the photocurable composition containing the quantum dots between two barrier layers and subsequently curing the photocurable composition by photoirradiation.
  • the wavelength and the irradiation dose of the light to be irradiated at the time of forming the wavelength conversion layer can be set as appropriate in accordance with the formulation of the photocurable composition.
  • an ultraviolet light having a wavelength of 280 nm to 400 nm is irradiated at an irradiation dose of 100 mJ/cm 2 to 5,000 mJ/cm 2 .
  • Examples of an ultraviolet light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and an ultraviolet light emitting diode (UV-LED).
  • a low-pressure mercury lamp a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and an ultraviolet light emitting diode (UV-LED).
  • UV-LED ultraviolet light emitting diode
  • the wavelength conversion layer may be formed in the form of a film that has two main surfaces facing each other, and an end surface surrounding the periphery of the main surfaces.
  • an average thickness of the wavelength conversion layer which corresponds to the height of the end surface, may be, for example, 30 ⁇ m to 200 ⁇ m, preferably 30 ⁇ m to 150 ⁇ m, or 80 ⁇ m to 120 ⁇ m.
  • the average thickness is 30 ⁇ m or more, the wavelength conversion efficiency tends to be further improved, whereas when the average thickness is 200 ⁇ m or less, a backlight unit tends to be further reduced in thickness by applying the wavelength conversion layer to the backlight unit.
  • the average thickness of a film-form cured product can be determined as, for example, an arithmetic mean value of the thickness measured at arbitrary three spots using a reflection spectroscopic film thickness meter or the like.
  • the laminate is configured such that barrier layers are each laminated on one of the main surfaces of the wavelength conversion layer and on the other main surface.
  • barrier layers from the standpoint of inhibiting a reduction in the emission efficiency of the quantum dots, for example, barrier films having an inorganic layer can be used.
  • the barrier layers may have an average thickness of, for example, 20 ⁇ m to 150 ⁇ m, preferably 20 ⁇ m to 120 ⁇ m, or 25 ⁇ m to 100 ⁇ m.
  • the average thickness of the barrier layers can be determined in the same manner as that of the wavelength conversion layer in the form of a film.
  • the barrier layers preferably have a barrier property against oxygen.
  • the barrier layers may have an oxygen permeability of, for example, 0.5 mL/(m 2 ⁇ 24 h ⁇ atm) or less, preferably 0.3 mL/(m 2 ⁇ 24 h ⁇ atm) or less, or 0.1 mL/(m 2 ⁇ 24 h ⁇ atm) or less.
  • the oxygen permeability of the barrier layers can be measured at a temperature of 23° C. and a relative humidity of 65% using an oxygen permeability measuring device (e.g., OX-TRAN manufactured by MOCON Inc.).
  • the barrier films having an inorganic layer that constitute the barrier layers may each include, for example, a substrate film, and an inorganic layer arranged on at least one main surface of the substrate film. Further, the barrier layers may each be, for example, a laminated film that includes two substrate films, and an inorganic layer arranged between the two substrate films.
  • thermoplastic resins such as polyester (e.g., polyethylene terephthalate and polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethyl pentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, methyl polymethacrylate, polycarbonate, and polyurethane.
  • the material constituting the substrate film is preferably, for example, polyester or cellulose triacetate.
  • the substrate film may have an average thickness of, for example, 10 ⁇ m to 150 ⁇ m, preferably 20 ⁇ m to 125 ⁇ m.
  • the average thickness of the substrate film is 10 ⁇ m or more, the generation of wrinkles and the occurrence of breakage during assembling and handling of the wavelength conversion member are effectively inhibited. Meanwhile, when the average thickness is 150 ⁇ m or less, the substrate film can contribute to a weight reduction and a thickness reduction of an image display device.
  • the substrate film may be composed of a single film, or may be a laminated film composed of plural films.
  • Such a laminated film depending on the intended use thereof, may be composed of plural layers that are formed of films made of the same constitutent raw materials, or may be composed of plural layers that are formed of films made of different constituent raw materials.
  • the inorganic layer may be a film formed of an inorganic compound, such as an oxide, a nitride, an oxynitride, or a carbide.
  • the inorganic compound include: metal oxides, such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides, such as aluminum nitride; metal carbides, such as aluminum carbide; oxides of silicon, such as silicon oxide, silicon oxynitride, silicon oxycarbide, and silicon oxynitrocarbide; nitrides of silicon, such as silicon nitride and silicon nitrocarbide; carbides of silicon, such as silicon carbide; and hydrides of these inorganic compounds.
  • the inorganic layer may be composed of a single kind of inorganic compound, or two or more kinds of inorganic compounds.
  • the inorganic layer may have an average thickness of, for example, 10 nm to 200 nm, preferably 10 nm to 100 nm, or 15 nm to 75 nm.
  • the inorganic layer may be formed by any known method in accordance with its constituent materials.
  • the known method include: plasma CVD methods, such as CCP-CVD and ICP-CVD; sputtering methods, such as magnetron sputtering and reactive sputtering; vacuum deposition methods; and vapor deposition methods.
  • the barrier layers constituting the laminate may each have a first modification part on at least a portion of their end surfaces.
  • the first modification part may have, on its surface, at least one oxygen-containing functional group (hereinafter, also simply referred to as “functional group”) selected from the group consisting of a carboxy group, a hydroxy group, and a carbonyl group.
  • functional group oxygen-containing functional group
  • the presence of a functional group on the surface of the first modification part can be identified by, for example, measuring an infrared absorption spectrum on the surface of the first modification part.
  • the infrared absorption spectrum can be measured by, for example, an attenuated total reflection (ATR) method using a Fourier transform infrared spectrophotometer (e.g., manufactured by Thermo Fisher Scientific K.K.).
  • the first modification part can be formed by, for example, applying an energy to the respective barrier layers.
  • the content of a functional group in the first modification part can be evaluated by, for example, measuring an infrared absorption spectrum on the surface of the first modification part.
  • the ratio (I 1 CO /I 1 CH ) on the surface of the first modification part may be, for example, 0.1 to 30, preferably 0.5 or higher, 1 or higher, 5 or higher, 7 or higher, or 9 or higher, but preferably 20 or lower, 15 or lower, 14 or lower, 12 or lower, or 11 or lower. Further, the ratio (I 1 OH /I 1 CH ) on the surface of the first modification part may be, for example, 0.1 to 10, preferably 0.2 or higher, 0.4 or higher, 0.6 or higher, or 0.8 or higher, but preferably 5 or lower, 4 or lower, 2 or lower, 1.5 or lower, or 1.2 or lower.
  • the intensity ratio of the peak attributed to CO stretching vibration and that of the peak attributed to OH stretching vibration on the surface of the first modification part is in the above-described respective numerical ranges, the moisture components contained in the ambient air and the like are likely to bind with CO groups and OH groups on the surface of the first modification part. As a result, the intrusion of the moisture components contained in the ambient air and the like into the wavelength conversion member can be effectively inhibited.
  • the barrier layers have the first modification part on their end surfaces, and a region other than the first modification part is a non-modification part that is not modified.
  • the non-modification part may be, for example, a region where an energy for the formation of the first modification part is not applied.
  • the content of a functional group may be less than the content of the functional group in the first modification part. In other words, a ratio of the content of a functional group in the first modification part with respect to the content of the functional group in the non-modification part may be higher than 1.
  • the non-modification part may be a region that is away from the end surface of each barrier layer by a prescribed distance in the direction parallel to the main surface of the barrier layer, for example, a region that is away from the end surface by 5 mm or more, preferably 10 mm or more, or 20 mm or more. Further, the non-modification part may be the end surface of each barrier layer prior to the formation of a singulated laminate using a laser beam in the below-described production method. It is noted here that the first modification part may be a region within a distance of 10 ⁇ m, preferably 9 ⁇ m from the end surface of each barrier layer in the direction parallel to the main surface of the barrier layer.
  • a ratio of the intensity of a peak corresponding to the hydroxy group in the first modification part with respect to the intensity of a peak corresponding to the hydroxy group in the first non-modification part may be higher than 1, preferably 1.03 or higher, 1.05 or higher, or 1.1 or higher, but 20 or lower, 10 or lower, 5 or lower, 2 or lower, or 1.2 or lower.
  • a ratio of the intensity of a peak corresponding to the carbonyl group in the first modification part with respect to the intensity of a peak corresponding to the carbonyl group in the first non-modification part may be higher than 1, preferably 1.1 or higher, 1.2 or higher, or 1.25 or higher, but 20 or lower, 10 or lower, 5 or lower, 2 or lower, or 1.5 or lower.
  • the intensity of the peak corresponding to the hydroxy group may be a ratio of the intensity of a peak attributed to OH stretching vibration based on the intensity of a peak attributed to CH stretching vibration
  • the intensity of the peak corresponding to the carbonyl group may be a ratio of the intensity of a peak attributed to CO stretching vibration based on the intensity of a peak attributed to CH stretching vibration.
  • the first modification part may be, for example, a thermally denatured product of the thermoplastic resin constituting the barrier layers. It is believed that, by forming the end surface of the laminate using a laser beam as in the below-described method of producing a wavelength conversion member, the thermoplastic resin constituting the barrier layers is thermally denatured and the first modification part is thereby formed.
  • the first modification part may be formed on at least a portion of the end surface of each barrier layer, or may be formed on the entirety of the end surface of each barrier layer.
  • the wavelength conversion layer constituting the laminate may have a second modification part on at least a portion of its end surface.
  • the second modification part may have, on its surface, at least one oxygen-containing functional group (hereinafter, also simply referred to as “functional group”) selected from the group consisting of a carboxy group, a hydroxy group, and a carbonyl group.
  • functional group oxygen-containing functional group
  • the presence of a functional group on the surface of the second modification part can be identified by, for example, measuring an infrared absorption spectrum on the surface of the second modification part in the same manner as on the surface of the first modification part.
  • the second modification part can be formed by, for example, applying an energy to the wavelength conversion layer.
  • the content of a functional group in the second modification part can be evaluated by, for example, measuring an infrared absorption spectrum on the surface of the second modification part.
  • the ratio (I 2 CO /I 2 CH ) on the surface of the second modification part may be, for example, 0.1 to 30, preferably 0.2 or higher, 0.4 or higher, 0.8 or higher, 1 or higher, or 1.2 or higher, but preferably 15 or lower, 10 or lower, 6 or lower, 4 or lower, or 2 or lower.
  • the ratio (I 2 OH /I 2 CH ) on the surface of the second modification part may be, for example, 0.1 to 10, preferably 0.2 or higher, 0.3 or higher, but preferably 5 or lower, 4 or lower, 3 or lower, 2 or lower, 1 or lower, 0.8 or lower, or 0.6 or lower.
  • the moisture components contained in the ambient air and the like are likely to bind with CO groups and OH groups on the surface of the second modification part. It is believed that, as a result, the intrusion of the moisture components contained in the ambient air and the like into the wavelength conversion member can be effectively inhibited.
  • the wavelength conversion layer has the second modification part on its end surface, and a region other than the second modification part is a non-modification part that is not modified.
  • the non-modification part may be, for example, a region where an energy for the formation of the second modification part is not applied.
  • the content of a functional group may be less than the content of the functional group in the second modification part. In other words, a ratio of the content of a functional group in the second modification part with respect to the content of the functional group in the non-modification part may be higher than 1.
  • the second non-modification part may be a region that is away from the end surface of the wavelength conversion layer by a prescribed distance in the direction parallel to the main surface of the wavelength conversion layer, for example, a region that is away from the end surface by 5 mm or more, preferably 10 mm or more, or 20 mm or more. Further, the non-modification part may be the end surface of the wavelength conversion layer prior to the formation of a singulated laminate using a laser beam in the below-described production method. It is noted here that the second modification part may be a region within a distance of 10 ⁇ m, preferably 9 ⁇ m from the end surface of the wavelength conversion layer in the direction parallel to the main surface of the wavelength conversion layer.
  • a ratio of the intensity of a peak corresponding to the hydroxy group in the second modification part with respect to the intensity of a peak corresponding to the hydroxy group in the second non-modification part may be higher than 1, preferably 1.2 or higher, 2 or higher, or 2.4 or higher, 2.6 or higher, 2.8 or higher, or 3 or higher, but 8 or lower, 7 or lower, 6 or lower, 5 or lower, or 4 or lower.
  • a ratio of the intensity of a peak corresponding to the carbonyl group in the second modification part with respect to the intensity of a peak corresponding to the carbonyl group in the second non-modification part may be higher than 1, preferably 1.2 or higher, 1.6 or higher, 2 or higher, or 2.4 or higher, but 8 or lower, 7 or lower, 6 or lower, 5 or lower, or 4 or lower.
  • the intensity of the peak corresponding to the hydroxy group may be a ratio of the intensity of a peak attributed to OH stretching vibration based on the intensity of a peak attributed to CH stretching vibration
  • the intensity of the peak corresponding to the carbonyl group may be a ratio of the intensity of a peak attributed to CO stretching vibration based on the intensity of a peak attributed to CH stretching vibration.
  • the second modification part may be, for example, a thermally denatured product of the cured resin constituting the wavelength conversion layer. It is believed that, by forming the end surface of the laminate using a laser beam as in the below-described method of producing a wavelength conversion member, the cured resin constituting the wavelength conversion layer is thermally denatured and the second modification part is thereby formed.
  • the second modification part may be formed on at least a portion of the end surface of the wavelength conversion layer, or may be formed on the entirety of the end surface of the wavelength conversion layer.
  • the second modification part may be at least partially exposed on the end surface of the laminate.
  • the second modification part exposed on the end surface of the laminate may have an average thickness of 10% to 80%, preferably 20% to 70%, or 20% to 60%, with respect to the average thickness of the wavelength conversion layer.
  • the thickness of the second modification part means the height of the second modification part in the lamination direction of the laminate.
  • the ratio of the average thickness of the second modification part exposed on the end surface of the laminate with respect to the average thickness of the wavelength conversion layer is determined by measuring the thickness of the exposed second modification part at arbitrary three spots, and calculating an arithmetic mean of values obtained by dividing the measured values by the average thickness of the wavelength conversion layer, in terms of percentage.
  • the end surface of the laminate may be formed such that the first modification part, the second modification part, and the first modification part are laminated in this order.
  • the first modification part may cover at least a portion of the boundary between each barrier layer and the wavelength conversion layer on the end surface of the laminate.
  • the wavelength conversion member can be configured such that discoloration from its end portion is more effectively inhibited.
  • the length of the boundary covered by the first modification part may be 1% or more, preferably 10% or more, or 100%, with respect to a total length of the boundary on the end surface of the laminate.
  • the first modification part may further cover a portion of the wavelength conversion layer.
  • the portion of the wavelength conversion layer that is covered may be a portion of the second modification part, or an unmodified portion of the wavelength conversion layer.
  • the coverage ratio of the portion of the wavelength conversion layer that is covered by the first modification part may be, for example, 5% to 50%, preferably 5% to 30%, or 5% to 10%, in terms of the ratio of the area of the portion of the wavelength conversion layer that is covered by the first modification part with respect to the area of the wavelength conversion layer that is calculated from the length of the end surface of the laminate and the average thickness of the wavelength conversion layer.
  • FIG. 3 is a schematic cross-sectional view that schematically illustrates one aspect of a cross-section of an end portion of a wavelength conversion member 100 , which cross-section is parallel to the lamination direction.
  • the wavelength conversion member 100 is constituted by: a wavelength conversion layer 20 ; and barrier layers 10 each arranged on two main surfaces of the wavelength conversion layer 20 .
  • a first modification part 18 is formed in an end portion of each barrier layer 10
  • a second modification part 28 is formed in an end portion of the wavelength conversion layer 20 .
  • a thickened part 16 which is formed by an increase in the thickness of each barrier layer, and air bubble parts 12 which are formed by a gas generated due to laser beam irradiation are formed.
  • the thickened part 16 is configured such that the main surface of each barrier layer, which is on the opposite side of the wavelength conversion layer side, expands in the lamination direction.
  • the thickened part 16 By the formation of the thickened part 16 in the end portion of the wavelength conversion member 100 , the water vapor permeability to the side of the end portion can be further reduced.
  • the end portion of the laminate has penetration pathways of moisture in the lamination direction and the direction perpendicular to the lamination direction, and is thus a region that is likely to be exposed to moisture; however, by the formation of the thickened part 16 , the intrusion of moisture can be effectively inhibited.
  • the formation of the air bubble parts 12 in the first modification part 18 for example, even when a stress is applied to the end portion of the wavelength conversion member 100 , delamination of the wavelength conversion layer 20 and the barrier layers 10 can be inhibited by a buffering action derived from the air bubble parts 12 .
  • a stress may be unintentionally applied to the end portion of the wavelength conversion member during, for example, transport of the wavelength conversion member, or integration of the wavelength conversion member into a backlight device or the like.
  • the formation of the air bubble parts 12 a difference in refractive index is created in each barrier layer, as a result of which the light scattering property of the wavelength conversion member may be improved.
  • a protruding part 14 which protrudes to the outer side than the wavelength conversion layer may be formed.
  • the protruding part 14 may be formed as a part of the first modification part 18 .
  • the contact area between the end surface of the laminate and the end surface covering layer is increased, so that the adhesion of the end surface covering layer to the laminate is further improved.
  • the wavelength conversion member may further include an end surface covering layer that covers the end surface of the laminate.
  • the end surface covering layer may be, for example, a member that is configured to contain an inorganic material and has a gas barrier property.
  • the end surface covering layer may also be a member that inhibits the intrusion of moisture, oxygen, and the like from the end surface of the laminate.
  • the end surface covering layer may be arranged to cover at least a portion of the end surface of the laminate, and may be preferably arranged to cover the whole end surface of the laminate over the entire circumference.
  • the end surface covering layer may include, for example, the film exemplified above as an inorganic layer, which is formed of an inorganic compound such as an oxide, a nitride, an oxynitride, or a carbide. Particularly, from the standpoint of gas barrier property and high refractive index, a silicon compound such as silicon oxide, silicon nitride, silicon oxynitride, or silicon carbide may be used.
  • the end surface covering layer may be composed of a single kind of inorganic compound, or two or more kinds of inorganic compounds.
  • the end surface covering layer may include a cured resin layer that is formed of a resin composition containing at least one functional material selected from the group consisting of the below-described moisture removers (moisture scavengers), oxygen removers (oxygen scavengers), antioxidants, and the like.
  • the resin composition may contain, for example, an epoxy resin as a matrix.
  • the average thickness of the film in the direction perpendicular to the end surface of the laminate may be, for example, 0.05 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.9 ⁇ m, or 0.1 ⁇ m to 0.8 ⁇ m.
  • the average thickness of the cured resin layer may be, for example, 5 ⁇ m to 1,000 ⁇ m, preferably 200 ⁇ m to 800 ⁇ m, or 300 ⁇ m to 650 ⁇ m.
  • the thickness of the end surface covering layer is, for example, the distance between the outermost end of the end surface covering layer and the end surface of the laminate when the laminate is viewed from above.
  • the cured resin layer may have a uniform thickness along the lamination direction of the wavelength conversion member, or may have an increasing or decreasing thickness toward one direction.
  • the end surface covering layer may be formed by any known method in accordance with its constituent materials.
  • the film formed of an inorganic compound can be formed by a plasma CVD method such as CCP-CVD or ICP-CVD, a sputtering method such as magnetron sputtering or reactive sputtering, a vacuum deposition method, a vapor deposition method, or the like.
  • the end surface covering layer includes a cured resin layer
  • the cured resin layer can be formed by applying a desired resin composition to the end surface of the laminate, and subsequently curing the resin composition.
  • FIG. 8 is a schematic cross-sectional view of a wavelength conversion member 110 , which illustrates one example of the end surface covering layer.
  • An end surface covering layer 30 illustrated in FIG. 8 is a cured resin layer that is formed of a resin composition containing an epoxy resin and at least one functional material selected from the group consisting of moisture removers (moisture scavengers), oxygen removers (oxygen scavengers), and antioxidants.
  • the end surface covering layer 30 is provided on both sides of the opposing end surfaces of the wavelength conversion member 110 .
  • the end surface covering layer 30 may be provided on the entirety of the end surface surrounding the outer circumference of the wavelength conversion member 110 .
  • the end surface covering layer 30 is arranged across the two barrier layers 10 and the wavelength conversion layer 20 , covering at least the boundary between the barrier layer 10 positioned above and the wavelength conversion layer 20 , as well as the boundary between the barrier layer 10 positioned below and the wavelength conversion layer 20 .
  • the intrusion of moisture and the like through the boundaries between the respective barrier layers 10 and the wavelength conversion layer 20 can be more effectively inhibited.
  • the upper end of the end surface covering layer 30 is positioned higher than the boundary between the barrier layer 10 positioned above and the wavelength conversion layer 20 . In the end surface covering layer 30 illustrated in FIG.
  • the upper end of the end surface covering layer 30 is positioned between the upper surface of the barrier layer 10 positioned above and the upper surface of the wavelength conversion layer 20 , not reaching the upper surface of the barrier layer 10 positioned above.
  • the end surface covering layer 30 can be prevented from involuntarily creeping up to the upper surface of the barrier layer 10 at the time of arranging the end surface covering layer 30 , so that a reduction in brightness can be inhibited in the upper surface end portion of the laminate.
  • the lower end of the end surface covering layer 30 is positioned in substantially the same plane as the lower surface of the barrier layer 10 positioned below.
  • the end surface covering layer 30 has an inclined surface 32 that is inclined with respect to the upper surface of the barrier layer 10 positioned above.
  • the inclined surface 32 may be a flat surface, or may include a curved surface.
  • the end surface of the laminate may be a surface that is formed by cutting by laser beam irradiation, or may be a surface that is not cut by laser beam irradiation.
  • the end surface of the laminate may be a surface that is formed by cutting by laser beam irradiation.
  • the wavelength conversion member may also include a laminate including other layers.
  • the other layers include a hard coat layer, an optical compensation layer, a transparent conductive layer, an adhesion-imparting layer, and the below-described intermediate layer.
  • the laminate may include an intermediate layer that is arranged between the wavelength conversion layer and one barrier layer.
  • As the intermediate layer a member that exhibits good adhesion to both the wavelength conversion layer and the barrier layer may be selected. This enables to inhibit the intrusion of moisture and the like through, for example, the boundary between the intermediate layer and the wavelength conversion layer, and the boundary between the intermediate layer and the barrier layer.
  • the intermediate layer may contain, as a matrix, for example, a cured resin having the same composition as the cured resin exemplified above in the description of the wavelength conversion layer.
  • the intermediate layer may further contain at least one functional material in addition to the cured resin.
  • the functional material include moisture removers (moisture scavengers), oxygen removers (oxygen scavengers), and antioxidants, and the intermediate layer may contain at least one selected from the group consisting of these functional materials.
  • moisture removers examples include: oxides of Group 2 elements, such as magnesium oxide and calcium oxide; hydrotalcites; aluminosilicates (e.g., zeolite); and silicon oxides (e.g., silica gel).
  • the hydrotalcites may be compounds having a composition represented by the following Formula (3):
  • M 3 represents a divalent metal ion, such as Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+
  • M 4 represents a trivalent metal ion, such as Fe 3+ , Cr 3+ , Co 3+ , or In 3+
  • a n ⁇ represents an n-valent anion, such as OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , NO 3 ⁇ , CO 3 2 ⁇ , SO 4 2 ⁇ , Fe(CN) 6 3 ⁇ , CH 3 COO ⁇ , an oxalate ion, or a salicylate ion
  • x satisfies 0 ⁇ x ⁇ 0.33
  • m represents a positive number.
  • oxygen removers examples include ceria-zirconia solid solution (CZ solid solution).
  • antioxidants examples include ascorbic acid, catechin, dibutylhydroxytoluene, tocopherol, and butylhydroxyanisole.
  • the content of the functional material in the intermediate layer may be, for example, 0.1 parts by mass to 20 parts by mass, preferably 0.1 parts by mass to 15 parts by mass, or 0.1 parts by mass to 2 parts by mass, with respect to 100 parts by mass of the cured resin.
  • the intermediate layer may have a thickness of, for example, 10 ⁇ m to 100 ⁇ m, preferably 20 ⁇ m or more, or 30 ⁇ m or more, but preferably 70 ⁇ m or less, or 40 ⁇ m or less.
  • a method of producing a wavelength conversion member may include: a first step of providing a laminated sheet that includes a wavelength conversion layer containing quantum dots, and two barrier layers each laminated on one of main surfaces of the wavelength conversion layer and on the other main surface; and a second step of cutting the laminated sheet by irradiation with a laser beam intersecting the main surfaces of the laminated sheet to obtain a singulated laminate.
  • the irradiation with a laser beam in the second step may be performed at a laser beam frequency of 5 kHz to 30 kHz, a scanning speed of 50 mm/s to 100 mm/s, and a laser beam output of 3.4 W to 100 W.
  • discoloration from an end portion can be inhibited in the resulting wavelength conversion member including the laminate. This is believed to be because, for example, by cutting the laminated sheet by the irradiation with a laser beam, the first modification parts derived from the respective barrier layers and a second modification part derived from the wavelength conversion layer are formed on an end surface of the laminate.
  • a laminated sheet which includes a wavelength conversion layer containing quantum dots and two barrier layers each laminated on one of main surfaces of the wavelength conversion layer and on the other main surface.
  • the laminated sheet can be produced, for example, in the following manner.
  • a first composition layer is formed by applying the above-described photocurable composition to a surface of a film-form barrier layer (e.g., a barrier film) that is continuously transported.
  • a method of applying the photocurable composition include a gravure coating method, a die coating method, a curtain coating method, an extrusion coating method, a rod coating method, and a roll coating method.
  • a film-form barrier layer e.g., a barrier film
  • a laminated sheet precursor in which the barrier layer, the first composition layer, and the barrier layer are laminated in this order is obtained.
  • a light is irradiated from the side of one of the barrier layers to cure the first composition layer and form a wavelength conversion layer, whereby a laminated sheet in which the barrier layer, the wavelength conversion layer, and the barrier layer are laminated in this order is obtained.
  • a drying treatment, a heat treatment, and the like may be performed on the first composition layer prior to the irradiation of the light. It is noted here that the details of the wavelength conversion layer and the barrier layers that constitute the laminated sheet are as described above.
  • the laminated sheet is cut by irradiation with a laser beam intersecting the main surfaces of the laminated sheet to obtain a singulated laminate.
  • the frequency of the laser beam may be, for example, 5 kHz to 30 kHz, preferably 5 kHz to 28 kHz, or 5 kHz to 25 kHz.
  • the output of the laser beam may be, for example, 3.4 W to 100 W, preferably 5 W to 50 W, or 5 W to 30 W.
  • the laser beam include a carbon dioxide gas laser, a UV laser, and a YAG laser, and a carbon dioxide gas laser may be used.
  • the cutting of the laminated sheet by the irradiation with the laser beam is performed by scanning the laminated sheet with the laser beam while allowing the laser beam to intersect the main surfaces of the laminated sheet.
  • the scanning speed of the laser beam may be, for example, 50 mm/s to 100 mm/s, preferably 60 mm/s to 100 mm/s, or 70 mm/s to 100 mm/s.
  • the number of scans with the laser beam per cut surface may be, for example, 1 to 5, preferably 1 to 2.
  • the irradiation of the laminated sheet with the laser beam may be performed while discharging an inert gas to the vicinity of an irradiation position of the laser beam.
  • an inert gas contamination of the resulting laminate by a decomposition gas can be inhibited.
  • the inert gas used for the discharge include a noble gas such as argon and a nitrogen gas, and a nitrogen gas may be used.
  • the amount of the inert gas to be discharged may be, for example, 100 ml/s to 1,000 ml/s, preferably 100 ml/s to 500 ml/s.
  • the laminated sheet to be irradiated with the laser beam may be maintained in a state of being in contact with a support, or in a state where at least the irradiation position of the laser beam is separated from the support.
  • the laminated sheet may be maintained in a state where at least the irradiation position of the laser beam is separated from the support.
  • the laser beam may be irradiated with space being provided on the side of the main surface of the laminated sheet that is opposite to the main surface irradiated with the laser beam.
  • the entirety of the laminated sheet portion including a region of the singulated laminate may be maintained such that it is spaced from the support, or a recess, a notch, or the like may be formed at a position of the support that corresponds to the irradiation position of the laser beam so as to maintain the laminated sheet such that a space is provided on the opposite side of the irradiation position of the laser beam.
  • a cut surface intersecting with the main surfaces constitutes an end surface.
  • the cut surface constituting the end surface of the laminate may be, for example, substantially perpendicular to the main surfaces of the laminate. Further, the cut surface may be formed in a manner to surround the periphery of the laminate.
  • the periphery of the laminate may be surrounded by four flat cut surfaces, or by cut surfaces including at least one curved cut surface.
  • the cut surface of the laminate On the cut surface of the laminate, at least a portion of the end surfaces of the two barrier layers constituting the laminate and at least a portion of the end surface of the wavelength conversion layer are exposed.
  • the cut surface By forming the cut surface such that at least a portion of the end surface of the wavelength conversion layer is exposed thereon, discoloration of the wavelength conversion member from an end portion with time is inhibited.
  • the details of the exposed state of the end surface of the wavelength conversion layer on the cut surface of the laminate are as described above.
  • a first modification part may be formed on at least a portion of the end surface of each barrier layer.
  • the first modification part may have, on its surface, at least one oxygen-containing functional group selected from the group consisting of a carboxy group, a hydroxy group, and a carbonyl group.
  • the details of the amount of the oxygen-containing functional group existing on the surface of the first modification part are as described above. Further, the density of the oxygen-containing functional group existing on the surface of the first modification part may be higher than the density of the oxygen-containing functional group existing on the end surfaces of the barrier layers of the laminated sheet prior to the cutting.
  • a ratio of the density of the oxygen-containing functional group existing on the surface of the first modification part with respect to the density of the oxygen-containing functional group existing on the end surfaces of the barrier layers of the laminated sheet prior to the cutting may be higher than 1, preferably 5 or higher.
  • the details of the ratio of the density of the oxygen-containing functional group existing on the surface of the first modification part with respect to the density of the oxygen-containing functional group existing on the end surfaces of the barrier layers of the laminated sheet prior to the cutting are as described above.
  • the first modification part may cover the boundaries between the respective barrier layers and the wavelength conversion layer.
  • the details of the covering state of the first modification part at the cut surface of the laminate are as described above.
  • a second modification part may be formed on at least a portion of the end surface of the wavelength conversion layer.
  • the second modification part may have, on its surface, at least one oxygen-containing functional group selected from the group consisting of a carboxy group, a hydroxy group, and a carbonyl group.
  • the details of the amount of the oxygen-containing functional group existing on the surface of the second modification part are as described above.
  • the density of the oxygen-containing functional group existing on the surface of the second modification part may be higher than the density of the oxygen-containing functional group existing on the end surface of the wavelength conversion layer of the laminated sheet prior to the cutting.
  • a ratio of the density of the oxygen-containing functional group existing on the surface of the second modification part with respect to the density of the oxygen-containing functional group existing on the end surface of the wavelength conversion layer of the laminated sheet prior to the cutting may be higher than 1, preferably 5 or higher.
  • the details of the ratio of the density of the oxygen-containing functional group existing on the surface of the second modification part with respect to the density of the oxygen-containing functional group existing on the end surface of the wavelength conversion layer of the laminated sheet prior to the cutting are as described above.
  • the barrier layers of the laminated sheet may contain a thermoplastic resin.
  • the first modification part formed on the cut surface of the laminate may contain a thermally denatured product of the thermoplastic resin that is generated at the time of cutting the laminated sheet with a laser beam.
  • the wavelength conversion layer of the laminated sheet may contain a cured resin of a photocurable composition.
  • the second modification part formed on the cut surface of the laminate may contain a thermally denatured product of the cured resin that is generated at the time of cutting the laminated sheet with a laser beam.
  • This alumina pot containing the raw materials was mounted on a ball mill rotating stand (AV-1; manufactured by AS ONE Corporation), and the raw materials were mixed at a rotation speed of 160 rpm for 48 hours. Subsequently, as an organic solvent, 50 g of hexane was added to the alumina pot containing the raw materials, and the raw materials were further mixed at a rotation speed of 160 rpm for 3 hours. After the completion of the mixing of the raw materials, the resulting mixture was passed through a nylon mesh having a mesh size of 300 ⁇ m by suction filtration to remove the zirconia balls YTZ, whereby a first mixture was obtained in the form of a slurry. This first mixture was suction-filtered and then air-dried for 24 hours in the air atmosphere to obtain a nanoparticle precursor.
  • AV-1 ball mill rotating stand
  • the thus obtained nanoparticle precursor had a composition represented by [(NH 2 ) 2 CH] PbBr 3 (hereinafter, also referred to as “FAPbBr 3 ”).
  • the nanoparticle precursor displayed orange color.
  • the nanoparticle precursor did not emit light even when irradiated with a light having a wavelength of 450 nm.
  • An XRD pattern of the above-obtained nanoparticle precursor was measured by X-ray diffraction (XRD) method using CuK ⁇ rays.
  • the measurement of the XRD pattern indicating the diffraction intensity (Intensity) with respect to the diffraction angle (2 ⁇ ) was performed using an X-ray diffractometer (MiniFlex, manufactured by Rigaku Corporation) under the below-described conditions. The result thereof is shown in FIG. 1 .
  • FIG. 1 shows the XRD pattern (top) of the nanoparticle precursor, and the XRD pattern (bottom) of FAPbBr 3 having an orthorhombic crystal structure, which is registered in ICSD (inorganic Crystal Structure Database).
  • ICSD inorganic Crystal Structure Database
  • the nanoparticle precursor in an amount of 3.15 g was added to a wet microbead mill pulverizer/disperser (LABSTAR Mini; manufactured by Ashizawa Finetech Ltd.) along with 0.94 g of oleylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.31 g of octadecyldimethyl (3-sulfopropyl)ammonium hydroxide (SBE-18; manufactured by Merck KGaA), and 101 g of toluene (manufactured by FUJIFILM Wako Pure Chemical Corporation) as organic solvents, and 422 g of zirconia balls YTZ having a diameter of 0.2 mm (yttria-stabilized zirconia; manufactured by AS ONE Corporation) as a dispersion medium, and the added materials were stirred for 1 hour at a circumferential speed of 14 m/sec and a rotation speed of 4,456 rpm.
  • oleylamine manufactured
  • a mixture obtained by this stirring was passed through a nylon mesh having a mesh size of 25 ⁇ m by suction filtration to remove the zirconia balls YTZ and unpulverized coarse nanoparticle precursor, whereby a second mixture was obtained in the form of a slurry.
  • the thus recovered supernatant was passed through a syringe filter having a pore size of 0.2 ⁇ m to obtain a dispersion containing nanoparticles.
  • the content of the nanoparticles in the dispersion was 0.57% by mass.
  • FIG. 2 shows a TEM image of the nanoparticles.
  • the average particle size of the nanoparticles was determined from TEM images captured at a magnification of ⁇ 80,000 to ⁇ 200,000.
  • a TEM grid a High Resolution Carbon HRC-C10 STEM Cu100P grid (manufactured by Okenshoji, Co., Ltd.) was used.
  • the above-obtained nanoparticles had a spherical shape or a polygonal shape.
  • the average particle size was determined by selecting TEM images of at least three spots, measuring the particle size for all measurable nanoparticles contained in the TEM images, and calculating the arithmetic mean of the thus measured values.
  • the average particle size of the nanoparticles was determined by measuring the particle size of each nanoparticle, which was defined as the length of the longest line segment among those line segments connecting any two points on the circumference of the particle observed in a TEM image and passing through the center of the particle, and calculating the arithmetic mean of the particle size of at least 100 nanoparticles.
  • the average particle size of the above-obtained nanoparticles was 11.2 nm.
  • a solution was prepared by mixing 5.0 g of the dispersion containing the nanoparticles (content of nanoparticles: 0.57% by mass) and 2.03 g of isobornyl acrylate (IBOA; manufactured by Tokyo Chemical Industry Co., Ltd.) as a radical polymerizable monomer. While heating this solution at 30° C. under a reduced pressure of 10 mbar using an evaporator, toluene was vaporized over a period of 24 hours to obtain a nanoparticle IBOA dispersion. The content of the nanoparticles in the thus obtained dispersion was 1.4% by mass.
  • IBOA isobornyl acrylate
  • Emission characteristics were measured for the thus obtained nanoparticle IBOA dispersion.
  • the nanoparticle IBOA dispersion was irradiated with a light having a peak emission wavelength of 450 nm to measure the emission spectrum at room temperature (25° C.).
  • the nanoparticle IBOA dispersion was diluted with a solvent (IBOA) such that the absorbance at 450 nm was adjusted to be 0.15. From the thus obtained emission spectrum, the internal quantum efficiency (%), the peak emission wavelength (nm), and the half-value width (nm) in the emission spectrum were determined.
  • the internal quantum efficiency (%) which is a ratio of photons converted to light emission among those photons absorbed by the nanoparticles, was calculated by dividing the number of emitted photons (%) by the number of absorbed photons (%).
  • the emission characteristics of the nanoparticle IBOA dispersion are shown in Table 1.
  • the nanoparticle IBOA dispersion exhibited a high emission efficiency with an internal quantum efficiency of 92%, had a narrow half-value width of 24 nm, and was excellent in color purity. Further, the nanoparticle IBOA dispersion had a peak emission wavelength of 518 nm, and absorbed a light having a peak wavelength of 450 nm to emit a green light.
  • An acrylic monomer mixed solution was obtained by mixing 0.7 g of dicyclopentanyl acrylate (FA-513AS; manufactured by Showa Denko Materials Co., Ltd.), 0.3 g of EO-modified bisphenol A dimethacrylate (FA-321M; manufactured by Showa Denko Materials Co., Ltd.), and 0.01 g of 2,4,6-trimethylbenzoyl phosphine oxide (TPO; manufactured by FUJIFILM Wako Pure Chemical Corporation) serving as a photopolymerization initiator.
  • FFA-513AS dicyclopentanyl acrylate
  • FA-321M EO-modified bisphenol A dimethacrylate
  • TPO 2,4,6-trimethylbenzoyl phosphine oxide
  • barrier films manufactured by i-Components Co., Ltd., TBF1004.
  • the photocurable composition was applied between these two barrier layers using a roll-to-roll applicator, and the resultant was irradiated with ultraviolet rays emitted from a UV irradiator to initiate a monomer polymerization reaction and cure the photocurable composition, whereby a laminated sheet in which the barrier films were adhered to both main surfaces of a wavelength conversion layer having a thickness of 50 ⁇ m was produced.
  • a laminate having a rectangular shape of 25 mm on one side (025 mm) was cut out using a carbon dioxide gas laser irradiator at a frequency of 25 kHz, an output of 7.5 W, and a scanning speed of 70 mm/s, in two passes per cross-section, whereby a wavelength conversion member of Example 1 was produced.
  • a wavelength conversion member of Example 2 was produced in the same manner as in Example 1, except that the output of the carbon dioxide gas laser irradiator was changed to 15 W.
  • a wavelength conversion member of Example 3 was produced in the same manner as in Example 1, except that the output of the carbon dioxide gas laser irradiator was changed to 30 W.
  • a wavelength conversion member of Comparative Example 1 was produced by cutting out a laminate having a rectangular shape of 25 mm on one side (025 mm) from the above-obtained laminated sheet using a cutting machine.
  • an SEM image was obtained as a reflected electron image of a cut surface under a scanning electron microscope (SEM; JSM-IT200 manufactured by JEOL Ltd.) at an acceleration voltage of 5 kV and a probe current of 50 ⁇ A.
  • FIG. 4 shows the thus obtained reflected electron image of a cut surface of the wavelength conversion member of Comparative Example 1, which cut surface was obtained using a cutting machine
  • FIG. 5 shows the thus obtained reflected electron image of a cut surface of the wavelength conversion member of Example 3, which cut surface was obtained using a laser.
  • FIG. 6 shows the thus obtained fluorescence micrograph of the cross-section of the end portion of the wavelength conversion member according to Comparative Example 1, which cross-section was obtained using a cutting machine
  • FIG. 7 shows the thus obtained fluorescence micrograph of the cross-section of the end portion of the wavelength conversion member according to Example 3, which cross-section was obtained using a laser.
  • a sample having a modified cut surface was prepared by cutting under the laser irradiation conditions of Example 3.
  • an infrared absorption spectrum was measured by an attenuated total reflection (ATR) method using a Fourier transform infrared spectrophotometer (manufactured by Thermo Fisher Scientific K.K.).
  • a peak intensity ratio attributed to CO stretching vibration I 1 CO /I 1 CH
  • a peak intensity ratio attributed to OH stretching vibration I 1 OH /I 1 CH
  • a peak intensity ratio attributed to CO stretching vibration I 2 CO /I 2 CH
  • a peak intensity ratio attributed to OH stretching vibration I 2 OH /I 2 CH
  • a ratio (I 1 CO /I 2 CO ) of the peak intensity ratio attributed to CO stretching vibration in the first modification part with respect to the peak intensity ratio attributed to CO stretching vibration in the first non-modification part, as well as a ratio (I 1 OH /I 2 OH ) of the peak intensity ratio attributed to OH stretching vibration in the first modification part with respect to the peak intensity ratio attributed to OH stretching vibration in the first non-modification part were calculated. The results thereof are shown in Table 2.
  • the acrylic monomer mixed solution prepared in Reference Example 1 was irradiated with ultraviolet rays under the same conditions as in Reference Example 3 to obtain a cured product.
  • the thus obtained cured product was cut under the laser irradiation conditions of Examples 2 and 3 to obtain samples having a modified cut surface.
  • an infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (manufactured by Thermo Fisher Scientific K.K.).
  • a peak intensity ratio attributed to CO stretching vibration I 3 CO /I 3 CH
  • a peak intensity ratio attributed to OH stretching vibration I 3 OH /I 23 CH
  • a peak intensity ratio attributed to CO stretching vibration I 4 CO /I 4 CH
  • a peak intensity ratio attributed to OH stretching vibration I 4 OH /I 4 CH
  • a peak intensity ratio attributed to CO stretching vibration I 5 CO /I 5 CH
  • a peak intensity ratio attributed to OH stretching vibration I 5 OH /I 5 CH
  • the wavelength conversion members of Examples 1 to 3 and Comparative Example 1 were evaluated in the following manner.
  • the wavelength conversion members were left to stand in a thermo-hygrostat chamber (manufactured by ESPEC Corp.) under an atmosphere having a temperature of 60° C. and a relative humidity of 90%. After a lapse of 100 hours, the wavelength converting members were taken out of the thermo-hydrostat chamber and used as post-storage-test samples.
  • the wavelength conversion member according to one embodiment of the present disclosure is useful in light sources for various lighting devices, vehicles, displays, and the like. Particularly, the wavelength conversion member can be advantageously applied to backlight units of image display devices using a liquid crystal.

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